Overcoming copper-induced conversion reactions in nickel disulphide anodes for sodium-ion batteries.

Employing copper (Cu) as an anode current collector for metal sulphides is perceived as a general strategy to achieve stable cycle performance in sodium-ion batteries, despite the compatibility of the aluminium current collector with sodium at low voltages. The capacity retention is attributed to the formation of copper sulphide with the slow corrosion of the current collector during cycling which is not ideal. Conventional reports on metal sulphides demonstrate excellent electrochemical performances using excessive carbon coatings/additives, reducing the overall energy density of the cells and making it difficult to understand the underlying side reaction with Cu. In this report, the negative influence of the Cu current collector is demonstrated with in-house synthesised, scalable NiS2 nanoparticles without any carbon coating as opposed to previous works on NiS2 anodes. Ex situ TEM and XPS experiments revealed the formation of Cu2S, further to which various current collectors were employed for NiS2 anode to rule out the parasitic reaction and to understand the true performance of the material. Overall, this study proposes the utilisation of carbon-coated aluminium foil (C/Al) as a suitable current collector for high active material content NiS2 anodes and metal sulphides in general with minimal carbon contents as it remains completely inert during the cycling process. Using a C/Al current collector, the NiS2 anode exhibits stable cycling performance for 5000 cycles at 50 A g-1, maintaining a capacity of 238 mA h g-1 with a capacity decay rate of 8.47 × 10-3% per cycle.

Development and Evaluation of Sn Foil Anode for Sodium-Ion Batteries.

Metal foil electrodes are simple to prepare and have a high active material loading, making them well suited for the fabrication of inexpensive high-energy-density batteries. Herein, Sn metal foil is used as a binder- and conductive additive-free anode for sodium-ion batteries, achieving a high reversible specific capacity of 692 mAh g-1 and coulombic efficiency of 99% after 100 cycles at a rate of 0.1 C. During the first discharge process, the anode undergoes area expansion. It then splits into multiple parts during the first-charge process. Upon cycling, the separated parts reconnect and form a single piece with a porous and robust coral structure owing to the self-healing nature of the anode. A full cell with a Sn foil anode and Na3 V2 (PO4 )3 cathode shows a stable cycle life of 100 mAh g-1 for 300 cycles. Thus, the cracking or pulverization of the Sn anode is not the principal origin of poor cycling properties. The adopted strategy will promote the development and commercialization of high-capacity metal foil anodes that undergo volume changes during charge/discharge cycling.

Ultrahigh-rate nickel monosulfide anodes for sodium/potassium-ion storage.

Transition-metal sulfides have been extensively studied as anode materials for use in sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) due to their multi-electron reactions, high rate performance, and abundant available resources. However, the practical capacities of metal sulfides remain low due to conductivity issues, volume expansion, and the use of traditional carbonate electrolytes. To overcome these drawbacks, ether electrolytes can be combined with nanoparticle-based metal sulfide anodes. Herein, a nanoparticle-based nickel monosulfide (NiS) anode with high rate performance in the ether electrolytes of SIBs/PIBs was prepared by heating a mixture of nickel nanoparticles with sulfur. In SIBs, the NiS anode capacity was 286 mA h g-1 at a high current density of 100 A g-1, and excellent cycling performance was observed at 25 A g-1 with a capacity of 468 mA h g-1 after 1000 cycles. Moreover, a full-cell containing a Na3V2(PO4) cathode demonstrated a rate performance of 65 mA h g-1 at a high current density of 100 A g-1. In PIBs, the NiS electrode capacity was 642 and 37 mA h g-1 at 0.5 and 100 A g-1, respectively. Hence, the synthesised NiS nanoparticles possessed excellent storage capability, regardless of the alkali-ion type, suggesting their potential use as robust NiS anodes for advanced battery systems.

Realizing High-Performance Li/Na-Ion Half/Full Batteries via the Synergistic Coupling of Nano-Iron Sulfide and S-doped Graphene.

Iron sulfide (FeS) anodes are plagued by severe irreversibility and volume changes that limit cycle performances. Here, a synergistically coupled hybrid composite, nanoengineered iron sulfide/S-doped graphene aerogel, was developed as high-capacity anode material for Li/Na-ion half/full batteries. The rational coupling of in situ generated FeS nanocrystals and the S-doped rGO aerogel matrix boosted the electronic conductivity, Li+ /Na+ diffusion kinetics, and accommodated the volume changes in FeS. This anode system exhibited excellent long-term cyclability retaining high reversible capacities of 422 (1100 cycles) and 382 mAh g-1 (1600 cycles), respectively, for Li+ and Na+ storage at 5 A g-1 . Full batteries designed with this anode system exhibited 435 (FeS/srGOA||LiCoO2 ) and 455 mAh g-1 (FeS/srGOA||Na0.64 Co0.1 Mn0.9 O2 ). The proposed low-cost anode system is competent with the current Li-ion battery technology and extends its utility for Na+ storage.

Binder-free and high-loading sulfurized polyacrylonitrile cathode for lithium/sulfur batteries.

Sulfurized polyacrylonitrile (SPAN) is a promising active material for Li/S batteries owing to its high sulfur utilization and long-term cyclability. However, because SPAN electrodes are synthesized using powder, they require large amounts of electrolyte, conducting agents, and binder, which reduces the practical energy density. Herein, to improve the practical energy density, we fabricated bulk-type SPAN disk cathodes from pressed sulfur and polyacrylonitrile powders using a simple heating process. The SPAN disks could be used directly as cathode materials because their π-π structures provide molecular-level electrical connectivity. In addition, the electrodes had interconnected pores, which improved the mobility of Li+ ions by allowing homogeneous adsorption of the electrolyte. The specific capacity of the optimal electrode was very high (517 mA h gelectrode -1). Furthermore, considering the weights of the anode, separator, cathode, and electrolyte, the Li/S cell exhibited a high practical energy density of 250 W h kg-1. The areal capacity was also high (8.5 mA h cm-2) owing to the high SPAN loading of 16.37 mg cm-2. After the introduction of 10 wt% multi-walled carbon nanotubes as a conducting agent, the SPAN disk electrode exhibited excellent cyclability while maintaining a high energy density. This strategy offers a potential candidate for Li/S batteries with high practical energy densities.

Free-Standing NiS2 Electrode as High-Rate Anode Material for Sodium-Ion Batteries.

Owing to the speculated price hike and scarcity of lithium resources, sodium-ion batteries are attracting significant research interest these days. However, sodium-ion battery anodes do not deliver good electrochemical performance, particularly rate performance. Herein, we report the facile electrospinning synthesis of a free-standing nickel disulfide (NiS²) embedded on carbon nanofiber. This electrode did not require a conducting agent, current collector, and binder, and typically delivered high capacity and rate performance. The electrode delivered a high initial capacity of 603 mAh g-1 at the current density of 500 mA g-1. Moreover, the electrode delivered the capacity of 271 mAh g-1 at the high current density of 15 A g-1. The excellent rate performance and high coulombic efficiency of the electrode were attributed to its low charge transfer resistance and unique structure.

High power Na3V2(PO4)3 symmetric full cell for sodium-ion batteries.

Sodium-ion batteries (SIBs) are a viable substitute for lithium-ion batteries due to the low cost and wide availability of sodium. However, practical applications require the development of fast charging sodium-ion-based full-cells with high power densities. Na3V2(PO4)3 (NVP) is a bipolar material with excellent characteristics as both a cathode and an anode material in SIBs. Designing symmetric cells with NVP results in a single voltage plateau with significant specific capacity which is ideal for a full cell. Here we demonstrate for the first time a tremendous improvement in the performance of NVP symmetric full cells by introducing an ether-based electrolyte which favors fast reaction kinetics. In a symmetric full cell configuration, 75.5% of the initial capacity was retained even after 4000 cycles at 2 A g-1, revealing ultra-long cyclability. Excellent rate performances were obtained at current densities as high as 1000C, based on the cathode mass, revealing ultrafast Na+ transfer. The power density obtained for this NVP symmetric cell (48 250 W kg-1) is the best among those of all the sodium-ion-based full cells reported to date.